Nitrogen containing esters



Patented Dec. 3, 1935 UNITED STATES PATENT OFFICE aozao'is mrnooan comammo as'mas Benjamin B. Harris, Chicago, 111.

No Drawing. Application January 11, 1934,

Serial No.

Claims.

My invention relates to a new class of chemical substances. .It relates more in particular to a class of chemical substances having the properties of interface modifiers when employed in a treating bath.

The object of my invention is the provision of a new class of chemical substances.

Another object is the provision of a class of chemical substances adapted for use as interface modifiers.

Still another object is the provision of a treating bath employing the new interface modifiers of my invention.

The class of substances of my invention has many useful applications in the arts where frothing, wetting, penetrating, detergent, emulsifying and other interface modifying functions are required. I may use them in a treating bath which contains aqueous media such as water and reagents to treat textile fabrics, leather or ores. The reagents are a class of substances such as NazCOa and other alkalis and soaps to scour wool, dyes for textiles, color discharging agents such as Na sulphoxilate and sulphites, oil and sulphonated oils, castor oil, sulfonated fish oils for stufllng leather, fatty acids such as oleic acid and H2304 for are separation and other reagents which react on surfaces. or at interfaces of textiles, leather, fabrics, ores and the like.

The substances of my invention are in general possessed of at least two groups, one having a hydrophile function and the other having a lipophile function in the molecule. The hydrophile function is performed primarily by a nitrogenous group, in the form of a. quaternary ammonium radical, specifically a betaine halide radical. The lipophile group is a. group having a definite afllnity for oils and fats and comprises either an ankyl, ether, or ester group linked to the betaine halide. The ester group is in general a monoor di-fatty acid ester of a polyhydroxy substance wherein another hydroxy group of the polyhydroxy substance is esterified with the carboxylic group of the betaine. l

The compounds of my invention may be represented by the formula wherein "L" is alipophile group with at least four carbon atoms in the form of either an alkyl, ether or ester radical; the remaining portion of the molecule represents a betaine radical, X" is an anion, such as 01-, Br, 1-, N O 3-, OH-, 804-, acetate or some other convenient organic or inorganic anion, and N" is a pentavalent nitrogen 'whose three indicated valence bonds are satisfied by alkyl, aryl, or cyclic radicals. w

Irrespective of diflerences of composition or structure, all of the substances of my invention have this much in common in that all of them comprise the radical the. above general formula that the compounds 0 of my invention are betaine esters wherein the quaternary ammonium radical is the hydrophile group and performs the principal hydrophile function in the molecule, while the remaining part of the molecule comprises a lipophile group, 5 which performs the lipophile function in the. molecule. The concept that certain interface modifying agents perform their role by orientating themselves at the'water-oil interface or at water-air interface, or at interfaces of other 30 materials in which my substances are used as aids in treating baths to promote penetration and surface action in connection with dyeing, bleaching, scouring of textiles, fabrics, leather,

and ore separation, is apparently satisfied by the 35 structure of the compounds of my present in- .vention.

The following are examples of compounds com- I in'g within the class of substances of my invention: 40

(1.) Cholesteryl ester of betaine chloride (Carbocholesteroxy) methyl trimethylammo-v nium chloride.

45 o K I te b0 almito D. X? 0 Hrmtgfi nyridi um (3) Melissyl ester of betaine bromide B O warm (18) Dodecyl ester of betaine chloride (4) nunwgzg (19) Cholesteryl ester of betaine bromide (20) Mellssyl ester of betaine chloride. 0 Br o bocho (a) On El i-Q zithygmeg i o Inc om rfias n mc-o-fi-cnm 21) 11L-o -cmo 13:

g j o E i F (a) OuKa- H:- fiam n. -ocm-N dinium bromide c1 ("1) Cetyl ester of betalne chloride E cm 22 0a! 0-cm-cn 0- 0H CH (8) Octyl ester of betaine bromide o m'o-o- -ounn o nfi n- -on (as olmn-o-om-onro-cnrcm o- -cm-K 0 25 (9) Es --O- -CHa 01E: CPN/ H:CO-84E| cl L 1 (24) nop:-om-

Hl-O-Ofl 0 (.31 (m) HaO-O-lL-Oufla o 11 cm (25) H- 0- cm OH: 0 Han- E 0 cm 0 en. cm 40 (m u o n-tz-o- -cn x q o H: m -'o- -cHr-N-om CnHn- O H! ll CHI OH CB: 0 cm 0 on 0 c1 12 CuHn-O--CHr-k (28) cumr w-cm-cmcm-oi s-cml L] CHI o 0 01 CH: O E (2n o|1m- J-ocmcmo-1 :cmN-cm (1a) ounw- -o-cnr-cm-o- -om-N-c,m

can 0 t CnHzr- O-CH: Ol ('11 "i oi 01 (2s 0 E- -0-ocm1- -O-CH H on CH -CH 5 (14) Cu-H r0 r r cuarg o im o 0H OH 01 (15) CHa-13-4)-CHr-bH-CHr-O-GHs-(EH-CHr-O-JZ-CBQ-k 0 The numbers used are for the'purpose of simm C.H -O-!1GH -NCH; plifying reference to and identification of the Cm compounds, and do not indicate any characteristic 7 1 of the substances. 0 0H 0 cm From the above examples, the general struca a 1| ture of the compounds of my invention will at (17) WET once be more apparent. In each case, the been; tame radical comprises the hydrophile group or 7 sufiiciently reactive to form the molecule, in which one of the bonds nitrogen is satisfied by the radical I.

of the The lipophile group in each instance is either an alkyl, ether or an ester group. For example, in the second example hereinabove, number 2 of the list, the lipophilegroup is a palmityl group of the carbopalmitoxy radical. In other examples given, the lipophile group is an ester of a poly hydroxy substance such as glycerine or glycol. The alkyl lipophile group-may be the radical of substantially any aliphatic alcohol having four carbon atoms or more. For example, the following alcohols may be employed as sources of the alkyl lipophile group: butyl, amyl, hexyl, octyl, dodecyl, hexadecyl, octadecyl, oleyl, ceryl, melissyl, cholesteryl, sitosteryl, phytosteryl, etc.

The L of the formula may also be satisfied as previously noted by an ester or ether group, such as a fatty acid ester or alkyl ether of a polyhydroxy substance. The polyhydroxy substances employed may be hydroxycarboxylic acids, sugars, alcohols, sugar alcohols, glycols, polyglycols, glycerols, polyglycerols; in fact, substantially any substance having at least two esterifiable hydroxy I groups. Examples of some other polyhydroxy substances are as follows: mucic acid, tartaric acid, saccharic acid, gluconic acid, glucuronic acid, gulonic acid, mannonic 'acid, trihydroxyglutaric acid, glyceric acid, and the like, as well as of carboxyllc oxidation products of polyglycerols such as represented by the following formula 0 0H 0 II I A il HO-C- H-CHz-O-CHg- H-CHz-O-C'Hz- 0H xylose, sucrose, glucose, lactose, galactose, fructose, maltose, rhamnose, sorbitol, dulcitol, arabltol and other substances having free hydroxy groups.

Examples of acids which may be employed as a source of the fatty acid lipophile radical forming a part of the lipophile ester group are as follows: caproic acid, capric, capryllic, Valerie, butyric, abietic, melyssic, hydroxyst'earic, benzoic, benzoylbenzoic, naphthoic, toluic, palmitic acid, stearic, lauric, melissic, oleic, myristic, ricinoleic, linoleic acid or any fatty acid with at least four carbon atoms, mixed fatty acids derived from natural fats, oils, hydrogenated oils, waxes.

Examples of some of the tertiary amines which I use as a source of and for the purpose of forming the quaternary nitrogen in the betaine radicle are: pyridine, various picolines, quinoline, isoquinoline, quinaldines, dimethyl aniline, diethylaniline, triethyl amine, ethyldimethylamine, trimethylamine and other tertiary amines which are quaternary ammonium compounds.

.In general, my preferred method of making these substances is to react a tertiary amine, either aliphatic, cyclic or mixed aliphatic-aromatic, with a lipophile ester of monobromor monochloracetic acid. A specific illustration of such a method is as follows:

Example N0. 1.I prepare the substancemarked above No. 1, by the following method:

To 40 parts of cholesterol I add 12 parts of chloracetyl chloride in benzol as a solvent, and

I with 18 to 20 parts heat under reflux at from 7!) to 80 degrees centigrade untfl there is no more hydrochloric acid evolved. This givesthe intermediary cholesteryl chloracetate. I evaporate oi! the benzol and then add hot water to wash out I acetyl chloride. I separate the material from the hot water, washing several times and then I evaporate oil. the residual benzol and dry the product to eliminate moisture.

I then dissolve 20 parts of the cholesteryl chlorm acetate obtained above in 200 parts of dry toluene. To this mixture or solution are added 5 parts of trimethyl amine dissolved in 15 parts of absolute methyl alcohol in a tightly closed vessel. After standing at room temperature for about 5 two days, a colorless heavy powder, which has settled to the bottom of the vessel, is filtered oil. This is the cholesteryl ester betaine chloride. It

is then further purified, if desired, by washing out the excess of trimethylamine with methyl alco- 20 hol and then dried.

The resulting compound indicated by the number 1 appearing hereinabove is surprisingly hydrophillic in character despite its considerable lipophile group. It disperses readily in aqueous Lu media and is a very potent improver of the frying characteristics of oleomargarine in that it reduces the spattering o'f margarine during frying, and has other important properties as an interface modifier. 30

I can prepare the first intermediary, namely, the cholesteryl chloracetate, by heating 40 parts of cholesterol with a large excess of chloracetic acid, approximately 100% in excess of that required to react stoichiochemically to produce the chlorace- 3., tate. For example, I heat 40 parts of cholesterol of chloracetic acid at a tem- 145 degrees C., with constant perature of 140 to agitation by bubbling carbon dioxide through for about from two -'to three hours. The excess'of 40 chloracetic acid is then washed out with water several times and the product is then dried and reacted as above with trimethylamine in dry toluene.

Compounds Nos; 3, 'l, 8, 9, 11, 12, 13, 16, 17, 18, 5 19, 20, 22, 25, and 27, and other substances of my I invention, may be satisfactorily prepared by the above described-methods, varying the amount of reagents proportionately with the molecular weights of the specific intermediary used. I can prepare my chloracetates by taking the lipin containing the hydroxy group and heating it with a large excess of chloracetic acid as shown above, or I can prepare my chloracetate deriva-. tive of the lipin by taking the .lipin containing the hydroxy group and adding to it chloracetyl chloride approximately 10% in excess of that required to react stoichiometrically in a solvent such as benzol, and purify the intermediary by themethod outlined above, or by any other convenient method, and then proceed with-the other stage of the reaction as outlined.

In the following table, I give examples of carrying out the reaction by one method for certain compounds, indicating the compounds by the numbers which I have designated above. I do not, however, limit this invention to the specific method of preparing the above substances, as well as similar equivalent substances of my invention, but they may be varied within the skill of a synthetic organic chemist to obtain substantially the same results. For example, if I desire to obtain the betaine bromide derivative of my lipin, I use in place of chloracetyl chloride,

the excess chlor- 5,

bromacetyl bromide, in proportions approximately chemically equivalent to those outlined above.

blinz an inert olein. I separa gas through to produce the monote the excess glycerine and take Amount ol ii in chlorece- No. oi Amount of llpin group (in compound PM) Solvent or lip bromace- Nitro enous base 1 in cholesterol. BenzcL- 20 chglsgt ryl chlorace- 6 trlmethylamine n 1236 ehloracetyl chloride. 200 toluene 15 absolute methyl alcohol 3 40 melissyl alcohol. do. 25 melissyl bromacetate 5 trlgiethylamine 20 bromacetyl bromide. 200 toluene its absolute methyl alcohol 7 20 oetyl alcohol. do. 14 cetyl chloracetate 5 trilmethylemine n 10 chloraoetyl chloride. 20D toluene 15 absolute methyl alcohol 9 30 monomyristin. do. 30 monomyrlstin 15 ethyl dlmethylchloraeetate amine 20 chlorecetyl chloride. 300 toluene 12 88 amyl alcohol. do. 20 emyl chloracetate 14 trlmethylamine 12% chloracetyl chloride. 200 toluene 45 methyl alcohol 13 33 monostearyl ethylene do 45 monostearyl ethylene 20 trletbylamin'e glyco glycol bromaeetate 22 bromacetyl bromide. 400 toluene 16 octyl alcohol. do. 20 octyl chloracetate l2 triimethylamine n 125 chloracetyl chloride. 200 toluene 35 methyl alcohol 18 20 dodecyl alcohol. do. 11 dogetgyl chloraw 5 tigmethylamine l3 chlorecetyl chloride. 150 toluene 35 absolute methyl alcohol 19 40 cholesterol. do. 22 cholesteryl 5 trimethylamine bromacetate in 2 bromacetyl bromide. 200 toluene l5 absolute methyl alcohol 20 40 melissyl' alcohol. do. 23 melissyl bromacetate 5 trinii thylamine l2 chloracetyl chloride. 200 toluene l5 absolute methyl alcohol 22 16 mono-octyl ether of do. 17 mono-octyl ether 0! 5 trimethyiamine ethylene glycol ethylene glycol in chloracetate 12 chloracetyl chloride. 200 toluene l5 absolute 27 methyl alcohol 33 monooleyl ethylene do. 45 mono-oleyl ethylene 18 trimethylglyco glycol chloracetate amine in 12% chloracetyl chloride. 400 toluene 65 absolute methyl alcohol The above are general directi these compounds. trimethyl mercially in methyl alcoh ons for preparing In view of the fact that amine is a gas which appears comol solution, it is advisable to use it in this solvent. However, any other solvent may be used. Many of the quaternary ammonium d shown above, are sparing used and for this reason place of toluene as a so may use some other suitab methods of separation and puri used.

erivatives of the betaine type, as 1y soluble in the solvents they precipitate out. In lvent, as shown above, I le solvent. Many other fication may be In the case of compound No. 1'7, I can prepare the intermediar stearin and 20 parts of parts of monost 5 parts trimethy absolute methyl of toluene as a solven ordinary temperatures, and

any other Compoun ing 282 parts of oleic acid y by taking 35 parts monochloracetic acid, heat the mixture at a temperature of about to degrees C. for two or action is substantially excess of chloracetic aci eral times and then dry earin chlorace lamine dissolved in 15 parts of alcohol, using about 200 parts t, reacting for two days at then purifying said ove, or by three hours, until the recomplete, wash out the d wit-h hot water sevthe product. Then 20 tate is reacted with erine at 220 degrees C. for two hours, by bub- 350 parts of my mono-olein and react it at high temperatures, about 220 to 230 degrees C. with 280 parts of oleic acid, until practically all of the oleic acid goes into the reaction to produce the diolein. During the reaction the product is stirred by bubbling an inert gas through, such as carbon dioxide. I then take 45 parts of my diolein and heat it with 15 parts of chloracetic acid at a temperature of about 135 to 145 degrees C., passing carbon dioxide gas through again, to produce the diolein chloracetate. I eliminate the excess chloracetic acid by the method shown above, or by any other suitable method, and then I take 40 parts of the dry diolein chloracetate and react it in a solvent, such as 400 parts of toluene, with 5 parts of trimethylamine dissolved in 15 parts of absolute methyl alcohol for about two days. I separate the compound and purify by one of the methods discussed hereinabove.

Another convenient procedure for the preparation of the new substances of my invention is to treat the lipophile material comprising an esteriiiable free hydroxy group, such as for example cholesterol, dissolved or suspended in an excess of dry pyridine or any other tertiary amine, which will be shown later, with a halo acetyl halide such as, for example, chloracetyl chloride or any other halo acetyl halide, preferably diluted with an inert solvent such as, for example, dry ether or any other inert solvent, at a low temperature. The halo acetyl halide, disspasms solved in the inert solvent, isadded gradually and the reaction mixture is allowed to stand for fromithirty to forty-eight hours at room temperature. By thismethod the tertiary amine serves two purposes: first, it acts asa condensing agent in that it serves to remove from the sphere of reaction the halogen acid formed during the acetylation; in the example'shown above, it removes hydrochloric acid, and secondly, it forms the quaternary ammonium group. A- specific illustration of such a method is as follows:

I dissolve 124 parts (all parts are by weight) preparation 01' other substances of my invention, such as, for example, Nos. 2, 4, 5, 6, 10, 14, 15, 21, 23, '24, 26 and others although slight variations in the purification procedure may be applied if desired in instances where the physical characteristics of the product require it. I

In preparing these compounds; I vary the proportions in accordance with the specific substances which I use, but in approximately the same ratio as shown by the above example.

The following table fllustrates the principle of my method more specifically:

No. oi Amount of lipin in dry Amount of nl- Amount of halo acetyl compound ethyl ether in parts) trogenous base halide in inert solvent 2 48% eetyl alcohol. io pyridine. 4o bromaeetyl bromide in 300 ether. 7 200 dry ether. 4 75 cholesterol. do. 40 bromacetyl bromide in 460 ether. 200 dry ether. 5 75 cholesterol. 02 dimethyl 40 bromacetyl bromide in 460 ether. aniline. 200dry ether. 6 75 cholesterol. qulnaldine. 40 bromacetyl bromide in 450 ther. 200 dry ether. 10 20 hexyl alcohol. do. 22 chloracetyl chloride.

200 ether. 200 dry ether. 14 t1 monolauryl di- 40 qulnaidine: 22 chloracetyl chloride. ethylene glycol. dry ether. 350 at r. a

16 81 monopalmityl di- 80 quinaldinc. 22 chloracetyl chloride. lycerol. 120 dry other. 500 at or. 21 71 monostearine. 80 pyridine. 45 chlorecetyl chloride. 450 other. 200 dry ether. I

23 66 monocetyl di- 80 qulnaldine. 40 bromace'tyl bromide.

ethylene glycol. I 200 dry ether. 420 ether.

24 41 al he-alpha dl- 40 pyridine. 22 chloracetyl chloride.

utyl ether of dry ether. Iglycerine. 300 et er. I

71 monostearine. do. 22 chloracetyl chloride. 450 ether. 150 dry ether. 28 124 dlolein. do. 40 chloraeetyl bromide.

700 ether. 200 dry ether.

of diolein in a mixture of 300 parts of dry ethylether and 40 parts of dry pyridine. To this solution, chilled to zero degrees C. and maintained at this temperature, I add, gradually and With vigorous stirring, 40 parts of bromacetyl bromide dissolved in 200 parts of dry ethyl ether. I then cover this mixture to protect it from atmospheric moisture, allow it to come up to room temperature and let it stand two days at room temperature. I decant the supernatant liquid, discarding the residue. I now distill off the ether at low temperature, disperse the residue in 1000 parts of warm 2% sodium chloride solution and finally add 8% additional salt to throw out the product as a supernatant layer. I draw out the brine from under the supernatant layer and discard the brine. I then repeat the warm brine washing once more to remove further impurities, principally pyridine, and finally drive oil the water at a low temperature from the supernatant layer. The product is a practically clear oil of straw color. While it has both hydrophile and lipophile groups, it is predominantly lipophile; has only very slight, if any wetting-out powers; has a very marked viscosity reducing effect on chocolate mixes, and is a very effective frying promoter for oleomargarine. This product may be represented by Example No. 28 indicated hereinabove.

I can use the same general method for the .I may vary the procedure lnconnection with the manufacture of similar compounds within certain limits to produce the same results. The methods of purification may also be varied within the skill of a synthetic organic chemist. I have found in practice that the halo acetyl halide dissolved in the inert solvent should be added slowly and gradually, with stirring and cooling, to the mixture. of tertiary amine and lipin containing the free hydroxy group. In place of a halo acetyl halide, I may use the halo propionyl halide such as bromopropionyl' bromide, and similar equivalent low molecular weight halo acyl derivatives.

In place of pure substances such as cetyl alcohol, oleic acid, palmitic acid, stearic acid; as intermediaries in the'preparation of my lipophile substance,'I may use mixtures such as fatty acids of corn oil or olive oil, acids of fish oils, or the like, which contain a large proportion of oleic acid, as well as many other fatty acids. I may also use mixtures of palmitic and.-

stearic acids or mixtures of palmitic, stearic and myristic acids; in placeof pure lauric acid I may use the fatty acids of coconut oil which contain about 40% of lauric acid. In place of pure cetyl alcohol I may use a mixture of cetyl alcohol and octadecyl alcohol which is obtained. from spermaceti. In all cases, however, the general pro- 1' cedure is as outlinedabove.

What I claim as new and desire to protect by Letters Patent of the United States is: 1. A chemical compound having interface modifying functions and represented by the formula wherein "L is a lipophile group of the class consisting of alkyls, ethers and esters, and having at least four carbon atoms, X" is an anion, and "N represents a pentavalent nitrogen with the three indicated valence bonds satisfied by radicals of the class consisting of alkyls, aryls, and the radical of a heterocyclic ringof which the nitrogen is a member. I

2. A chemical compound having interface modifying'functions and represented by the formula wherein L is an alkyl group with at least four carbon atoms, X 'is a halogen, and R1, R2, and R3 are substantially non-lipophillic alkyl radicals, each of R1, R2, and R3 containing less than four carbon atoms.

3. A chemical compound having interface modifying functions, and represented by the formula X Bi wherein L is a relatively high molecular weight ester of a polyhydroxy compound, X is a halogen, and R1, R2, and R3 are substantially nonlipophillic alkyl radicals, each of R1, R2, and R3 containing less than four carbon atoms.

4. A chemical compound having interface modifying functions, and represented by the formula wherein L is a relatively high molecular weight ether of a polyhydroxy compound, "X" is a halogen, and R1, R2 and R3 are substantially nonlipophillic alkyl radicals, each of R1, R2, and R: containing less than four carbon atoms.

5. A chemical compound having interface modifying functions, and represented by the formula wherein L is a relatively high molecular weight fatty acid ester of a polyhydric alcohol, "X" is a halogen, and R1, R2, and R3 are substantially nonlipophillic alkyl radicals, each of R1, R: and R: containing less than four carbon atoms.

6. A chemical compound having interface modifying functions, and represented by the formula 3 i 1r0-( JCH:NR|

wherein "L is a relatively high molecular weight ether of a polyhydric alcohol, X is a halogen, and R1, R2, and R3 are substantially non-lipophillic alkyl radicals, each of R1, R2, and R3 containing less than four carbon atoms 7. A chemical compound having interface modifying functions, and represented by the formula wherein "L is a relatively high molecular weight fatty acid ester of glycerlne, X is a. halogen, and R1, R2, and R3 are substantially non-lipophillic alkyl radicals, each of R1, R2, and R3 containing less than four carbon atoms.

8. A chemical compound having interface modifying functions, and represented by the formula wherein L is a relatively high molecular weight ether of glycerine, "X" is a halogen, and R1, R2, and R3 are substantially non-lipophillic alkyl radicals, each of R1, R2, and R3 containing less than four carbon atoms.

9. A chemical compound having interface modifying functions, and represented by the formula wherein L is a relatively high molecular weight ether of a glycol, X is a halogen, and R1, R2, and R3 are substantially non-lipophillic alkyl radicals, each of R1, R2, and R3 containing less than four carbon atoms.

11. A chemical compound having interface modifying functions, and represented by the formula wherein L is a mono-fatty acid ester of a polyhydroxy substance, X is a halogen, and R1, R2, and R3 are substantially non-lipophillic alkyl radicals, each of R1, R2, and R3 containing less than four carbon atoms.

12. A pyridine derivative having interface modifying functions, and represented by the formula wherein L is a lipophile group with at least four carbon atoms, and X" is a halogen.

13. A pyridine derivative having interface modifying functions, and represented by the formula wherein L" is a relatively high molecular weight ester of a polyhydroxy substance, and X" is a halogen.

14. A pyridine derivative having interface modifying functions, and represented by the formula wherein "L" isa relatively high molecular weight ether of a polyhydroxy substance, and "x" is a halogen.

15. A pyridine derivative having interface modifying functions, and represented by the formula x HJLCM wherein L is a relatively high molecular weight fatty acid ester of a polyhydric alcohol, and 3" is a halogen.

16. A pyridine derivative having interface modifying functions, and represented by the formula wherein "U is a relatively high molecular weight ether of a polyhydric alcohol ,vynd "X" is a halogen.

17. A pyridine derivative ha ng interface modifying functions, and represented by theformula wherein "L" is a relatively high molecular weight fatty acid ester of a glycerine, and "X" is a halogen.

18. A pyridine derivative having interface modifying functions, and represented by the formula wherein L is a relatively high molecular weight ether of glycerine, and X is a halogen.

19. The substance 20. The substance 0 0 01 cm CI1 r O-CHr-CHQO CHs1 ICHa CH: 21. A chemical compound having interface modifying functions, and represented by the formula II L-O-C-CHPNE wherein L is a radical of a relatively high molecular weight ester of a polyhydroxy compound,

X is an anion, and N represents a pentavalent nitrogen with the three indicated valence bonds satisfied by radicals of the class consisting of alkyl and aryl groups, and the radical of a heterocyclic ring of which the nitrogen is a member.

22.- A chemical compound having. interface modifying functions, and represented by the formula wherein L is a radical of a relatively high mula molecular weight ether of a nolyhydroxy compound, "x" is an anion, and "N" represents a pentavalent nitrogen with the three indicated valence bonds satisfied by radicals of the class consisting of allwl and aryl groups, and the radical of a heterocyclic ring of which the nitrogen is a member.

23. A chemical compound having interface maldifying functions, and represented by the form a wherein L molecular weight fatty acid ester of a polyhydric alcohol,- X" is an anion, and N represents a pentavalent nitrogen with the threeindicated valence bonds satisfied by radicals of the class consisting of alkyl and aryl groups, and the radical of a heterocyclic ring of which the nitrogen is a member,

24. A chemical compound having interface modifying functions, and represented by the formula wherein L'is a radical of a relatively high molecular weight ether of a polyhydric alcohol, X" is an anion, and "N" represents a pentavalent nitrogen with the three indicated valence bonds satisfied by radicals of the class consisting of alkyl and aryl groups, and the radical of a heterocyclic 7 ring of which the nitrogen is a'member.

' modifying-functions and represented by the formula L-O-C-CHr-NE wherein "L is a radical of a relatively high molecular weight ether of glycerine, X is an anion, and N represents a pentavalent nitrogen with the three indicated valence bonds satisfied by radicals of the class consisting of alkyl and aryl, groups, and the radical of a heterocyclic ring of which the nitrogen is a member.

27. A chemical compound having interface modifying functions, and represented by the foro Ire-(Learns wherein L is a radical of a relatively high molecular weight fatty acid ester of aglycol, X? is an anion, and N represents a pentavalent nitrogen with the three indicated valence bonds satisfied by radicals of the class consisting of I alkyl and aryl groups, and the radical of a heterocyclic ring of which the nitrogen is a member. 28. A chemical compound comprising interis a radical of a relatively high face modifying functions, and represented by the formula wherein L is a radical of a relatively high molecular weight ether of a glycol, X is an anion, and N represents a pentavalent nitrogen with the three indicated valence bonds satisfied by radicals of the class consisting of alkyl and aryl groups, and the radical of a heterocyclic ring of which the nitrogen is a member.

29. A chemical compound having interface modifying functions, and represented by the formula O L-O--CHr-IhE wherein L" is a radical of a mono-fatty acid ester of a polyhydroxy substance, X is an anion, and N represents a pentavalent nitrogen with the three indicated valence bonds satisfied by radicals of the class consisting of alkyl and aryl groups, and the radical of a heterocyclic ring of which the nitrogen is a member.

30. A pyridine derivative having interface modifying functions, and represented by the formula wherein L is a lipophile group with at least four carbon atoms, and X" is an anion.

31. A chemical compound with interface modifying functions and having lipophile and hydrophile groups, said compound being represented by the formula wherein L comprises the lipophile portion of the molecule and has at least 8 carbon atoms, X is an anion, and N represents a pentavalent nitrogen with the three indicated valence bonds satisfied by radicals of the class consisting of alkyl and aryl groups, and the radical of a heterocyclic ring of which the nitrogen is a member.

32. An ester with interface modifying properties with lipophile and hydrophile groups and represented by the formula 0 r L [-0-L-CHz-NE wherein L is the lipophile portion of the molecule with at least four carbon atoms, X is an anion, w is an integer and N represents a pentavalent nitrogen with the three indicated valance bonds satisfied by radicals of the class consisting of alkyl and aryl groups and the radical of the heterocyclic ring, of which the nitrogen is a member.

34. An ester with interface modifying proper ties'for interfaces between aqueous media and non-aqueous media, with lipophile and hydrophile groups and represented by the formula wherein L is the lipophile portion of the molecule with at least four carbon atoms, X is an anion, w is an integer, and N" represents a pentavalent nitrogen with the three indicated valence bonds satisfied by radicals of the class consisting of non-lipophile alkyl radicals containing less than four carbon atoms and aryl groups, and the radical of the heterocyclic ring, of which the nitrogen is a member.

35. A betaine ester of an aliphatic alcohol having a lipophile radical with at least four carbon atoms.

36. A betaine ester of an aliphatic monohydric alcohol having at least four carbon atoms.

37. A betaine ester of a polyhydric alcohol wherein the hydrogen of a hydroxy group of the alcohol hasits hydrogen replaced by a lipophile radical with at least four carbon atoms.

38. A betaine ester of a polyhydric alcohol wherein a hydroxy group of the alcohol is esterified with an aliphatic carboxylic acid having at least four carbon atoms. I

39. A betaine ester of a polyhydroxy substance wherein at least two hydroxy groups of the polyhydroxy substance are esterified with aliphatic carboxylic acids having at least four carbon atoms.

40. A betaine ester of glycerine wherein the two remaining hydroxy groups of the glycerine are esterified with aliphatic carboxylic acids having at least four carbon atoms.

41. A chemical compound having interface modifying functions and represented by the formula wherein L is a radical of the class consisting of alkyl ethers, and alkyl esters, said ethers and esters having at least four carbon atoms and having lipophile properties, X is an anion, and N represents a pentavalent nitrogen joined to carbons by the three indicated valence bonds.

42. A chemical compound having, interface modifying functions and represented by the forwherein L is a radical of the class consisting of lipophile alkyls, ethers, and esters, said alkyls, ethers, and esters having at least four carbon ator'ns, X is an anion, N represents a pentavalent nitrogen joined to carbon by the three indicated valence bonds, and w is a small integer.

43. The substance having the following formula 44. A chemical compound having interface modifying functions comprising a lipophile group 2,038,070 a l 9 emtflnlnlat'le'esttmcarbonatomlinkedto eenssumsrmnmmanememeu thegroup heterocycllcrlngotwhlchthenltrozenlsamum 45."!he compound er claim 44 wherein the a polyhydroxy substance is of the class 5 through a polrhydron wbstI-nce. "2 being an, 8 7 1 9 78 7 glycerol and 90mm! anion, and the three indicated valence bonds of J R the"fl"belnasatisfledbrradlcalsottheclass Certificate of Correction latent N 0. 2,023,075. December 3,1935.

BENJAMIN R. HARRIS,

It is hereby certified that errors appear in the printed specification of the above numbered patent requiring correction as follows: Page 2, first column, line 35, strike out formula number 10 and insert instead the following:

o c: care-Lauri page 7, first column, lines 5, 15, 22, 32 and 40, claims 14, 15, 16, 17 and 18 respectively, strlke out the formula and insert instead the following:

9 a L-O-lr-CE-N I and that the said Letters Patent should be read with these corrections therein that the same may conform to the record of the case in the Patent Office.

Signed and sealed this 1st day of September, A. D. 1936.

[SEAL] q LESLIE FRAZER, Acting Commissioner qffatcnta. V 

